Substituted phosphorous containing alkyl thio methyl carboxylates

ABSTRACT

CERTAIN SUBSTITUTED PHOSPHOROUS CONTAINING ALKYL THIO METHYL CARBOXYLATES OF THE FORMULA   R2O-P(=S)(-R1)-S-Q   IN WHICH Q IS:   -R3-CO-O-CH2-X-R4   R3 IS ALKYLENE, C1-C4; X IS SULFINYL OR THIO AND R4 IS ALKYL, C1-C4; OR   (R4-X-CH2-O-CO-)2-R5-   IN WHICH X AND R4 ARE AS DEFINED AND R5 IS A TRIVALENT SATURATED HYDROCARBON, C1-C3;OR   (R7-N(-R6)-CO-)-R5(-CO-O-CH2-X-R4)-   IN WHICH X,R4 AND R5 ARE AS DEFINED AND R6 AND R7 ARE HYDROGEN, ALKYL C1-C6, ARYL, HALO OR CYANO SUBSTITUTED ALKYL OR   KYL OR TETRAHYDRO FURFURYL OR WHEN ARE TAKEN TOGETHER, AN ALKYLENE, C2-C6, ETHYLENEOXYETHYLENE OR ETHYLENETHIOETHYLENE GROUPS;OR   R8-O-CO-R5(-CO-O-CH2-X-R4)-   IN WHICH X,R4 AND R5 ARE AS DEFINED AND R8 IS ALKYL C1 TO C2 OR HALOGEN, ARYL, HALOARYL SUBSTITUTED DERIVATIVES THEREOF;OR   R4-X-CH2-O-C(O)-C(-CH2-CO-O-CH2-X-R4)2-   IN WHICH X AND R4 ARE AS DEFINED AND THE USE OF THESE COMPOUNDS AS INSECTIDES AND ACARICIDES.

3,822,272 Patented July 2, 1974 SUBSTITUTED PHOSPHOROUS CONTAINING ALKYL THIO METHYL CARBOXYLATES Charles Ke'zeria'n, O'rinda, Califi, assignor to Stautfer Chemical Company,-New York, N.Y.

No Drawing. Original application Nov. 8, 1967, Ser. No. 681,576, now Patent No. 3,562,362. Dlvided and this application Sept. 2, 1970, Ser. No. 69,089

Int. Cl. C07d 29/36 us. c1 260-29335 1 Claim ABSTRACT on'rnn n s'oLosUnn Certain substituted, phosphorous containing alkyl 'thio in which X and R are. as defined and R is a trivalent saturated hydrocarbon, C -C or LN R/ 7 R7 fi-o-onixa .0

in which X, R, and 1R -are as definedand R, and R, are hydrogen, 'alkyl C -C aryl, halo or'cyano substituted alkyl or aryl or tetrahyd-ro furfuryl or 'when R; and R are taken together, an alkylene, -C ethyleneoxyethylene or ethylenethioethylene groups; or 1 in which x, R, and mate a defined and IR, is alkyl c, to C or halogen, aryl, haloaryl substituted derivatives thereof; or

CHa -E-O-CH2XRI C(O)-O-CH2XR m-p-o-omxn.

in which X and R are as defined and the use of these compounds as insecticides and acaricides.

This application is a division of copending application Ser. No. 681,576, filed Nov. 8, |1967 now UJS. 3,562,362.

.This invention relates to certain novel phosphorous containing alkyl thio methyl carboxylates compounds and to their uses as insecticides and acar-icides.

More specifically, this invention pertains to compounds of the formula in which 7 R is selected from the group consisting of alkyl having from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms; and alkoxy having from 1 to 4 carbon atoms, preferably from E1 to 2 carbon atoms, and most preferably ethoxy;

R is an alkyl group having from 1 to 4 carbon atoms,

preferably from "1 to 2 carbon atoms, and most preferably ethyl;

Q is selected from the group consisting of:

in which R is an alkylene group having from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, X is selected from the group consisting of thio and sulfinyl, preferably thio, R is an alkyl group having from '1 to 4 carbon atoms,

preferably from '1 to 2 carbon atoms;

in which X and IR, are defined as above and R is a trivalent saturated hydrocarbon group having from 1 to 3 carbon atoms, preferably from "1 to 2 carbon atoms;

in which X, R, and R are defined as above and R and R are independently selected from the group consisting of hydrogen; alkyl having from 1 to 6 carbon atoms and aryl, preferably phenyl, substituted derivatives thereof wherein the substituents are selected from the group consisting of halogen, preferably c'hloro, and "tetrahydrofurfuryl and when R3 and (R are taken together,'a member selected from the group consisting of 3 alkylene having from 2 to 6 carbon atoms, ethyleneoxyethylene, and ethylenethioethylene; and

wherein X, R, and R are defined as above and R is selected from the group consisting of alkyl having from 1 to 6 carbon atoms, and substituted derivatives therein in which said substituents are selected from the group consisting of halogen, preferably chlorine, aryl, preferably phenyl, and haloaryl, preferably chlorophenyl; and

in which X and R are defined as above.

The compounds of this invention can be prepared by various processes which are also features of this invention. In the following formulas R R R R R R R and R are as previously defined and K is an alkali metal and Hal is chloro or bromo radical, preferably chloro.

(A) Compounds of the formula can be prepared in two steps according to the following general reaction:

il? l P-SK Hal-Ih- -0H H8l=CHzSR4 Compound A Compound B Compound C More specifically, in step 1, Compound A can be reacted with Compound B and then the intermediate reaction product, in step 2, can be reacted with Compound C. In the alternative, Compound B can be reacted with Compound C and the intermediate reaction product, in a second step, can be reacted with Compound A.

(B) By another process, compounds of the formula in which R is alkylene radical having from 2 to 3 carbon atoms can be prepared in two steps by the following general reaction:

Compound E Compound D Compound 0 in which R and R are selected from the group consisting of methyl provided that both R, and R cannot be methyl. More specifically, in step 1, Compound E can be reacted with Compound D and the intermediate reaction product can be reacted, in step 2, with Compound C. In the alternative, Compound C can be reacted with Compound D and then the intermediate reaction in a second step,- reacted with Compound E.-

(C) Compound of the formula product,

can be prepared in two steps according to the following general equation:

0 i i-011+ Ha1=c1nsm /PSK Hal-Rs R2 |C-OH H8l=CHzSR4 Compound A Compound F Compound 0 More specifically, the above reactions can be carried out by reacting Compound A with Compound F, in step 1, and then reacting, in step 2, 1 mole of the intermediate reaction product thereof with 2 moles of Compound C. In the alternative, 1 mole of Compound F can be reacted with 2 moles of Compound C'and then, as a second step, the intermediate reaction product thereof can be reacted with Compound A.

(D) Alternatively, compounds of the formula F0 CHgSR in which R is a trivalent saturated hydrocarbon group having from 2 to 3 carbon atoms, can be prepared in two steps according to the following general equation:

0 R1 S a P-SH l], 2(Hal-CH SR COH R20 R, 0

Compound E Compound G Compound 0 can be prepared by the processes described in part (C) with the exception that a compound of the formula 0 Rs LN Hal-Rt C-OH ll 0 Compound E 3,822 Compound H is substituted for Compound D why the processes'described in part (D) with the exception -that'a compound of the formula I r [no "B 5 i' Bz a 1 ii-o-on ti Compound I is substituted for Compound G." Compound H and I can be prepared by well known proced res, for example, by reacting a compound of I the formula 0 O i at Hal-Rf 0 01 l \O 0 --c it. it respectively, with an amine of the formula NH R1 (F) Compound of the formula R1 s i i-0 1 i -sq tt I 1 11 0 -(lJ=-0CH SR|- can be prepared bythe processes described in part (C) o with the exception that a compound of the formula o i'J-O-Rl 40 Hal-Ra Compound J 4,5 is substituted for Compound D; or they can be prepared by the processes described in Part (D) with the exception that a compound of the formula 0 %i /O s C0H i.

Compound K is substituted for Compound G. Compounds J and K can be prepared by well known procedures by reacting a compound of the formula it ti-ii Hal-Rs 0 or L 0 g R. ll 5 respectively, with an alcohol of the formula R OH (G) Compounds of the formula R1 S HaC-i'J-O-CHaSRt' I E"S-GC(O)-O-CH:SR 1130 H, -COCH:SR|

'6 canbe prepared in two steps according to the following general equation:

Accordingly, Compound A can be reacted with Compound L in a first step and then 1 mole the intermediate reaction product produced thereby reacted with 3 moles of Compound C. In the alternative, 3 moles of Compound C can be reacted with 1 mole of Compound L in a first step and then the intermediate reaction product produced thereby reacted with Compound A.

All the reactions set out above between Compound C with a compound or intermediate reaction product containing one or more carboxylic acid moieties are preferably carried out in a solvent and in the presence of an HCl or HBr acid acceptor which are well known in the art. The reaction can proceed Without heating or the reactions are exothermic, however, heating between about 50 to C. is preferable as such reduces the reaction time.

In those reactions in which Compound A or Compound E is a reactant the reaction proceeds readily with heating between about 50 and 80 C. in a solvent.

All of the reactions set out above should be carried out under anhydrous conditions. Examples of solvents are acetone, ether, halogenated hydrocarbons such as carbon tetrachloride, or a liquid aliphatic or aromatic hydrocarbon, such as hexane, benzene, xylenes or the like. The addition reactions to unsaturated compounds in some cases proceed vigorously, usually after an induction period of a few minutes. These addition reactions are preferably effected initially at below about 40 C., with the reaction mixture eventually being heated at about 60 C. for several hours to insure completion of the reaction. Reactions involving evolution of a hydrogen chloride or hydrogen bromide are, preferably effected in the presence of a hydrogen chloride or hydrogen brw mide acceptor, such as an organic tertiary nitrogen base such as pyridine or preferably triethylamine or K CO Bases which form a salt and water with the hydrogen chloride or bromide should not be used as water has a deleterious effect on the reactions.

When the reactions are complete, any precipitate formed can 'be filtered off and any solvent or other volatile material removed by distillation.

The compounds of subdivision A through F of the proceeding processes can be converted to their 'sulfinyl derivatives by reacting them with an oxidizing agent such as hydrogen peroxide preferably in the presence of a 'solvent such as glacial acetic acid. This reaction can be carried on conveniently at room temperature with cooling. Thus as a result of this conversion, the moiety -CH SR of these compounds is oxidized to the The compounds of this invention can be prepared in accordance with the teaching of the following illustrative examples:

EXAMPLE I Methylthiomethyl, 2-'(0,0-' diethyl phosphosdithio)1- methyl propionate C2Hs0 S CH3 0 i -SC zCH-PJOCHzSOHa CzHsO 41.3 g. (0.135 M) of B(0,0' diethylphosphorodithio) 1 methyl propionic acid and ml. acetone was treated EXAMPLE II Bis methylthiomethyl, a (0,0' diethylphosphorodithio) succinate 21150 CHr-fi-O-CHzSCH;

11.8 g. (0.05 M) of bis methylthiomethyl maleate and 12 g. (0.065 M) 0,0 diethylphosphoro dithioic acid and a trace of hydroquinone were heated to 60-65 'C. for 1-6 hours. The mixture was diluted with 100ml. benzene and washed with HaHCO solution, then with water. The organic layer was dried over anhydrous magnesium sulfate, then distilled under vacuum to remove solvent and volatiles. There was obtained 17 g. of a yellow oil having an N of 1.5344. Infrared spectra of the sample corresponds to the above structure. Calc. for C 'H O PS C, 34.2, H, 5.46, P, 7.3 2; Found: C, 33.71, H, 5.74, P, 8.62.

EXAMPLE III N,'N dimethyl, methylthiomethyl, 0: (0,0 diethylphosphorodithio) succinate 33 g. (0:1 mole) of N 'N dimethyl a (0,0' diethylphosphoro dithio) succinamic acid and 13.9 g. (0.1 mole) K 00 were added to 100m]. acetone. Monochlorodimethyl sulfide 9.6 g. (0J1 mole) was added, and the mixture stirred overnight, and finally refluxed for -2 hours. Benzene 200 ml. was added with sufficient water to separate the organic layer. This was washed with water, 5% NaOH, again with water, then dried over anhydrous MgSO, and distilled under vacuum (below 45 C.) to remove solvent and volatiles. There was obtained 30 g. of a tan oil N 1.5250. Infrared corresponds to the above structure. Calc. for C I-I 'NO PS C, 37.0; H, 6.22; P, 7.96; N, 3.6; S, 24.65. Found: C, 38.61; H, 6.59; P, 8.11; N, 3.12; S, 25.41.

EXAMPLE IV N, N dimethyl, methyl sulfinylme'thyl, a (0,0 diethylphosphorodithio) succinate 30 g. (0.08 mole) .N,N dimethyl, methylthiomethyl, a (0,0' diethylphosphorodithio) succinamate in 100 ml.

glacial acetic acid was treated dropwise over 1 hour with 9 ml. (0.08. mole) 30% H 0 keeping at room temperature with cooling. Stir overnight'at room temperature. Benzene 300 ml. and water 500 ml. were added. Separate the organic layer and wash with water till the washings are neutral, then dried over anhydrous Mg.SO filtered and distilled under vacuum to remove solvent and volatile. A low yield 12 g. of yellow oil was obtained N 1.5248. Infrared corresponds to the above structure, with a strong sulfoxide bond at 10.90 cmf EXAMPLE V Ethyl, methylthiomethyl, a (0,0 dimethylphosphorodithio)'succinate CHgO S 13 g. (0.063 M) of ethyl, methylthiomethyl moleate and 11 g. (0.07 M) of 0,0'-dimethylphosphorodithioric acid were mixed with ml. benzene and stored for 2 days. The mixture was washed with 5% HaHCO solution, then with water. The organic solution was dried over anhydrous magnesium sulfate and distilled under vacuum to remove solvent and volatiles. There was obtained 12.5 g. of a yellow oil, with an N of 1.5169. Infra red spectra corresponds to the above structure. Calc. for C H O PS P, 8.55; S, 26.5. Found: P, 8.24; S, 26.77.

Table I through Table V contains other compounds of this invention that can be prepared by the procedure described in Examples I-V.

TABLE I R1 S O i SR: O-CHIXR Com ound num 81 R; R: R: X R4 .119

1 Ethoxy- Ethyl. -CH7- S MethyL. 1. 5214 2.... .....do ..do... CH2CHa- S ...do..... 1.5212

3 ..do ..do... CH; S ...do..... 1.5140

HoH

4' ..do ..do... CH; S ...do..... 1. 5100 CH; H-

s do do Same 0 do. 1.5260

TABLE II 0 R1 8 E-O-CHgXR;

PS--Rs R 0 C0-CH XR Compound number R1 R5 R5 X B1 no" 6 Ethoxy.-. Ethyl... -CH- 8 MethyL. 1.5344

7 Methoxy.- MethyL. Same S ...do..... 1.5580

See footnotes at end of Table V.

TABLE V As previously stated the compounds of this invention are useful as insecticides, especially systemic type insecticides.

Insecticidal Evaluation Test.The housefly (HF) Musca domestica (Linn.) was subjected to evaluation tests for insecticides incorporating the compounds of the present invention.

Twenty-five female flies, three to five days old, were caged in cardboard mailing tubes 3%" in diameter 2 /8" tall. The cages were supplied with cellophane bottoms and coarse mesh nylon tops. Each cage was provided with food and water. The candidate toxicant was dissolved in a volatile solvent, preferably acetone. The solution was pipetted into a Petri dish bottom, allowed to air dry and placed in a cardboard mailing tube cage. The flies were continuously exposed to the known residue of the active compound in the cage. After twenty-four and forty-eight hours, counts were made to determine living and dead insects. The LD-50 values were calculated using well known procedures. The results of this insecticidal evaluation test is given in Table II under HF. The Lygus bug (LB) Lygus hesperus was treated similarly as the houseflies, except ten to twenty-five insects were used per cage. The caged insects were sprayed with the candidate compounds at various concentrations. After twenty-four and seventy-two hours, counts were made to determine living and dead insects. The LD-50 (percent) values were calculated. These values are reported under the column LB in Table II.

The insect species bean aphid (BA) Aphis fabae was also employed in the test for insecticidal activity. Young nasturtium plants were used as the host plants for the bean aphid. The host plant was infested with approximately 50 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested-plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are given in Table II under the column BA.

Acaricidal Evaluation Test.The two-spotted mite (2SM), Tetranychus telariaus (Linn.), was employed in tests for miticides. Young pinto bean plants in the primary leaf stage were used as the host plants. Theyoung pinto bean plants were infested with several hundred mites. Dispersions of candidate materials were prepared by dissolving 0.1 gram in ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.0175% v./v. Sponto 221, polyoxy-ethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.25% to 0.0008%. The test suspensions were then sprayed on the infested pinto bean plants. After seven days, mortalities of post-embryonic and ovicidal-forms were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with the candidate compounds. The LD-50 value was calculated using well-known procedures. These values are reported under the columns ZSM-PE and 2SM- Eggs in Table VI.

- ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were prepared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a concentration of 10 parts per million (p.p.m.). Immediately after the host plant was placed in the test solution it was infested with the test species. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD-SO value was obtained. Mortality was recorded after 72 hours.

The percentage of kill of each test species was determined by comparison with control plants placed in distilled water or untreated soil. The LD-SO values were calculated. These systemic test results are reported in Table VI under the columns BA-sym" and ZSM-sym.

TABLE VI Percent Percent Compound HF, A-sym, Sym. number grams LB p.p.m PE Eggs p.p.m.

Not tested.

As those in the art are well aware, various techniques are available for incorporating the active component or toxicant in suitable pesticidal compositions. Thus, pesticidal compositions canbe conveniently prepared in the form of liquids or solids, the latter preferably as homogeneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids solutions directly. However, the more common procedure is to employ dispersions of the toxicant in an aqueous media and such compositions may be produced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by dispersion in water, usually with the aid of surface active agents. The latter, which may be the anionic, cationic or nonionic types, are exemplified by sodium stearate, potassium oleate and other alkaline metal soaps and detergents such as sodium lauryl sulfate, sodium naphthlene sulfonate, sodium alkyl naphthalene sulfonate, methyl cellulose, fatty alcohol ethers, polyglycol fatty acid esters and other polyoxyethylene surface active agents. The proportion of these agents commonly comprises l-15% by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

I claim:

1. A compound of the formula in which R is selected from the group consisting of alkyl having 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms; R; is an alkyl group having from 1 to 4 carbon atoms; Q is in which X is selected from the group consisting of thio and sulfinyl, R is an alkyl group having from 1 to 4 carbon atoms, R is a trivalent saturated hydrocarbon group having from 1 to 3 carbon atoms, and R and R taken together are pentylene.

References Cited UNITED STATES PATENTS HENRY R. JILES, Primary Examiner G. T. TODD, Assistant Examiner US. Cl. X.R.

260-239 A, 239 EP, 239 BF, 243 B, 247.1, 347.2

UNITED STATES PATENT AND TRADEMARK ()FFIQE CERTIFICATE OF CGRREQIIGN PATENT NO. 3,822,272 DATED July 2, 1974 lN\/ ENTOR(S) Charles Kezerian and" read

read

read

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 64, after the insert ---cyan0; and---.

Table III, under the heading HS".

Table III, under the heading "cyanoethyl".

Table III, under the heading "cyclohexyl".

Column 14, line 14, the word [SEAL] AIIeSI.

RUTH C. MASON Arresting Officer Words preferably chloro,

"X", Compound N0 12 should "R (imnpound No, 23 should R Compound N00 24 should "are" should read "is".

Signed and graded this twentieth 6f January 1976 (I. MARSHALL DANN (mnmr'ssimrer oflatenrs and Trademarks 

